Waterproof portland-cement mortar and process of making the same.



106. COMPOSITIONS,

COATING R PLASTIC To all whom it may concern:

Cross Reference PATENT OFFICE.

RICHARD H. GAINES, OF NEW YORK, N. Y.

WATERPROOF PORTLAND-CEMENT MORTAR AND PROCESS OF MAKING THE sum.

Be it known that I, RICHARD H. Games, a citizen of the United States, residing at New York, in the county and State of New York, have invented certain new and useful Impdrovements in Waterproof Portland-Cement ortar and Processes of Making the Same, of

- which the following is a specification.

My invention relates to the production of a waterproof, Portland cement mortar, which is particularly adapted to h draulic engineering works and various ot er structures requiring a waterproof concrete of maximum strength.

The object of my invention is to roduce an impermeable, yet inexpensive, ortland cement mortar, when. em loying clean sand, and without the intro uction of abnormal amounts of free alkalies or appreciable amounts of waterproofing, organic compounds of a bituminous, resinous, oily, fatty or albuminous nature. Such compounds act as binders or fillers and usually in a few years, at best, oxidize, become brittle and orous, break down, and thus entirely lose t eir effectiveness for waterproofin purposes.

It has long been known (first observed by the Rogersbrothers in the last century) that when certain finely powdered minerals are treated with water, reactions take place which result in partial decomposition. Concerning this fact, investigation with the inicroscope has shown, that water produces a colloidal surface-condition of the particles,-

leading to plasticity in the wet mass and increasing the binding power on induration. The latter change is due to the surface of the particles becomlng clogged with the products of hydrolytic decom osition.

By the addition of electrolytes to the water with which powderedminerals, such as feld spars, were treated, it has been found (Cush man) that an increased amount of decomosition products passed into solution. In act the same quantit of soluble decom osition products was 0 tained from a sly ground feldspar by treatment with a dilute solution of ammonium chlorid, as couldbe extracted by electrolysis without subsequent regrinding. However, the clogging effect of insoluble aluminium silicate, which is precipitated in a colloidal form on the sui'face of the particles, has been found to occasion the slowing up of hydrolysis on finely ground feldspar. The effect produced by dilute -so- Specification of Letters Patent.

Application'flled October'SB, 1907. Serial be static or ionic."

Patented March 31, 1908.

mesa-ass. If 67 lutions of salts is 1 principally to set free the roducts o hydrolysis, otherwise abthe colloidal decomposition prodthus expose fresh surfaces to the soluble sorbed nets, and solvent.

A study of the phenomena in connection with the coagulation of colloids by certain solutions indicates in the case of many metallic hydrates that the coagulating wer of electrolytes added to colloids is muc greater with polyvalent than with monovalent ions. Also researches on contact electricity, demonstrate that infinitesimal traces of certain ions, and especially of acids (hydrogen ions) render electrically neutral matters positive] charged when in neutral water, even thoug but one five-millionth part of acid is-added. The neutral liquids themselves also become charged, thus entirel changing the equilib rium conditions. he pecuhar behavior of colloids, moreover, indicates .that the same are electrically charged, in many cases the particles being positive and the liquid negative. The sign of the charge, however, ap ears to vary both with the nature of the co oid and according to the size of the particle. Upon the neutralization of the respective charges coagulation of the colloids occurs and dissolution ensues. I hecharge may My experiments have led to the discovery, that cement decomposition reactions, which in general are dprecisely similar altho h more pronounce can be augumented in t e same manner, namely by replacing the mixing water with a very ilute solution, preferably a one per cent. solution, of a suitable electrolyte-some substance the free charged ions of which would bring about a rearran ment of the molecules of the bodies with which they come in contact, thuscausing a complete change in the-equilibrium conditions of the system.

Aluminium sulfate is peculiarly for rep aclng e nnxing water in t e manner above stated, when in sufficiently dilute.

EXAMINE! adapted solution, preferably one er cent. solutions, as this sa t is capable of Being readily recipitated as a colloidal 'precipitate w en neutralized with alkaline oxids, such for example as the calcium 'd normal] resent in cement and also th1s salt, owing 5 its lnstablllfy, possesses weak acid reactions.

Moreover the greater electrical charge of the trivalent aluminium ions is particularly idea of the law of mass action).

effective in increasing its coagulating ower as compared with monovalent ions. 11 addition to these three properties above mentioned aluminium sulfate is particularly ada ted for this purpose, both because of its rea y solubility and also because of the extremel low cost of the same.

Witliout departing from the spirit of the invention as herein claimed, it is apparent that colloiding agents, other than aluminium sulfate, but ossessing similar properties, particularly its slightly acid pro erties as distinguished from the powerfu acid properties of strong mineral acids, its pre-' ci itation by alkaline oxids, such as calcium oxid, and its ready solubility may be used. The term sesqui-oxid-forming, as used in the claims, embraces various compounds which are useful ip this connection and the expression a COllOlCllIlg agent, capable of forming an insoluble precipitate wlth the calcium oxid normally present in the cement, and having weak acid properties is also used as having somewhat broader Slg'Illficance than the expression a compound of a sesqui-oxid-forming metal, and yet covering compounds which are also useful for th1s pur ose in greater or less degree.

I the complex series of changes that take place in the setting of cement, be 1nterpreted in the light of the electrolytic d1ssociation theory, the conclusion is reached that the following consecutive reactions occur in the wet mass: (1') Hydrolytic dlssociation, i. e. dissociation under the action of ions of water. (2) Formation of colloidal films about the particles, that act as osmotic membranes, ermeable to the lons of electrolytes. (3) A sorption of the basic ions by the hydrogels (inorganic collo ds) resulting in coagulation. (4) Recombination of dissociated molecules, tending to equilibrium.

In the setting of cement it is evident therefore that, the hydrolytic decomposition of cement by a suitable electrolyte indicates that the electrolyte forms, with,

some constituent of the system, compounds too unstable to exist under the conditions, Which compounds immediately break up, leaving the ions of the electrolyte free to react with fresh ortions of the-system, a process repeating itself. to a state of equilibrium. The presence of an electrolyte, therefore, causes a very different set of conditions from that existing in its absence conditions that impart to the concrete the desired properties of impernieability in addition to increased strength. This result of the introduction of the electrolyte may be summarized as follows: (1) By changing the equilibrium'conditions of t e system. (2) By increasing the quantities of reacting substances 'in the mass. (The fundamental (3) y settin free the basic ions absorbed by the colloi al decomposition products, thus exposing increased surface to the action of the solvent. t) By catalysis or electrical action set up in the mass by the excess of free ions, thus inducing chemical action.

The important role played by the colloidal decomposition products of cement as above described indicates that the process of setting is lar ely due to the coa ulation of inorganic co oids, and that the slowness of the action is in consequence of the indolence with which changes are prone to take place in these bodies. Indeed the simple crystallization of calcium hydroxid or other compounds, cannot give rise to the great increase in strength.

As is well known (see Clays: Henry Reiss) colloidal clays, as distinguished from many common cla s which are usually considered. non-colloidal owing to their small content of ingredients which are capable of assuming the colloid state by the action of Water alone, are of a highly plastic nature and consist of heterogeneous molecular com leXes. Subb microscopically, the colloidal c ays ossess a micellian structure, that is to say, t ey possess a web-like, porous formation, one of the distinguishing characteristics of which is the peculiar relation to, and dependency on, the water with which they are brou ht in contact, which they exhibit. When finely divided they are capable of freely flowing through -small dies or fine filter papers, which are capable of preventing the passage oflfinely divided nonlastic common clays containing but relative y small amounts of colloidal matter. As a result of further experiments during these observations I have discovered that the addition of inorganic colloids (hydro- 5 els such, for example, as sedimentary coloidal clay, which is capable of entering into a peculiar, hydrated, non-crystalline condition, and actuating as a negative catalyzer, serves to retard or su press the precipitation 1 of the scarcely solul le salts, owing to the fact that they unite easily with the said salt and tend to form molecular aggregates, without necessarily being precipitated.

The homogeneous admixture of the finely divided colloidal cla with the cement, prior to the amnd, enables one to not only secure uniform results but is important in thatthe sand is free from an occluding layer of clay and therefore necessarily capa ble of effectively uniting with the cement particles. In fact one of the chief objections to the use of dirty sand is the entire absence of uniformity and the decrease in ultimate strength in a large number of cases due to the insulation of the surfaces of the individual sand particles b clay or loam to Which the sand is virtua ly inert. The colloidal clay particles when admixed with the cement particles, especially minute particles 13o COATING OR PLASTlQ Cross Reference varying from one-five thousandths to onetwo hundred and fifty thousandths of an inch, become homogeneously and intimately united with the cement particles and upon 'the addition of water, the same is readily absorbed and the articles assume a gelatinous coating gradual y being converted into a coherent condition whereby the mass is rendered impervious. It is'evident that this peculiar affinity of colloidal claly for water, will cause the mass to swell ant entirely fill 'up 'all pores and voids in the cement mass, and since there is a limit to the amount of water absorbed by the clay, the introduction of the clay is in no way detrimental to the ultimate strength of the cement mass. In fact, entirely apart from any waterproofing properties which colloidal clay im arts to concrete, it' is decidedly beneficia in all cases for increasin the tensile and compression strengths, and in this it differs from the irregular effects roduced by common clays containing but iittle colloldal matter, as heretofore determined by previous investigators. Thus, in the setting of cement, the colloids perform a most useful function and increase the time of action, whereby a gradual evolution of heat is obtained. Since the amount of available energy in the form of heat produced in a chemical reaction is a constant, whether the reaction takes place slowly or not, it is evident that the presence of suitable colloids is one of vital importance inthe hardening of cement, as by the specific interaction of colloids and electrolytes, the calcium compounds normally present in the cement are protected from rapid hydration and the consequent increase in v0 ume, which will result from any excessiverise in temperature.

In order that others skilled in the art may make use of my invention I will now proceed to describe the exact manner by which I obtain a properly balanced mixture of colloids and electrolytes in the mortar aste, whereby, when hardened, I seeure a ense, impermeable mortar of maximum strength, especially applicable for making concrete.

In order to produce a one-to-three-mortar I take one hundred pounds of neat ordiy w which 1 intimately mix during e r0 ess of grinding fifteen to 'tlrirt pounds 0 imentarycolloidal cla suc for example, as that occurring on liong Island, New York, alon the Sound, or along the east shore of the Hu son. a

This cement-colloidal clay mixture, when sufiici'ently ground to reduce the articles to standard size, for example, of su cient fineness to permit to pass through a No. 200 sieve, is mixed with from 285 to 270 pounds of clean, sharp sand in accordance with the customary s ecilicatious, and to the mixture is then ad ed a solution containing one pound of aluminium sulfate per hundred weight, which solution entirely replaces the usual mixing water, and the proper amount of the solution to be added is determined in exactly the same manner as is the mixing water under the present methods of hydrolysis of cement.

It is evident that the mortars thus produced will be one-to three-mortars, owing to the fact that the amount of clay introduced replaces an equal amount of sahrl, for example, when 15 pounds of clay are present in the cement mixture, but 285 pounds of sand are mixed therewith, and if the clay is increased to thirty pounds a corres onding reduction in the amount of sand ad ed, namely 270 pounds is made.

The strength ofthe electrolyte should in no case exceed five per centum, and since greater concentrations than 1% are not further ionized, this latter-concentration is preferably employed.

The waterproof Portland cement mortar produced by my process is particularly applicable for the manufacture of concrete (beton) by admixture with the customary amounts of broken stone or rubble, either with or without suitable reinforcing bars, as twisted or corrugated steel bars. Moreover, contrary to expectations, there is an entire absence of-corrosion of the reinforcing bars or other iron work envelopedin concrete made .according to my rocess. Of course the broken stone may e mixed with the sand, prior to the addition of-the cement-colloidal clay com ound, if desired or prior to the addition 0 the dilute electrolyte solution, without departing from the spirit of my invention.

I am aware that it has been proposed to add to cement mortars suflicient amounts of Waterproofing organic compounds of a bit nous, resinous, oil ,fatty, or albuminous nature, to impart waierproofing properties to the cement mortar thus obtained. Also that it has beenattempted to produce a waterproof cement mortar by the addition of free acids and alkalies, 1n excess of the amount which normally occurs in ordinary Portland cement. In fact one of the chief distinctions between my cement mortar and those heretofore produced which were possessed of any appreciable waterproof qualities, lies in the absence of these yery gempounds and the seemingly slight variation frofiu'ie' standard s ecifications commonly used.

It is evi ent that without' departing from the spirit of my invention as claimed that either the clay may be omitted or on the other hand the electrolyte may be omitted and the clay-cement mixture and mixing water may be used in lieu thereof. In both cases I am enabled to obtain improved results, and practical impermeability, although preferably the combination of these two waterproofing agents is employed.

EXAMINER Having thus described my" invention, I claim:

1. The process of. making waterproof Portland cement mortar, which consists in first intimately mixing in a dry condition, ordinary Portland cement and an unburnt inorganic colloid, then mixing the same with sand in the presence of a dilute solution of a soluble salt of a sesqui-oxid-forming metal, and then permitting the. mass to set, substantially as described,

2. The process of making Waterproof Portland cement mortar, which consists in first intimately mixing in a dry condition, ordinary Portland cement and unburnt sedimentary colloidal clay, then mixing the'same with sand in the presence of a dilute solution of a soluble salt of a sesqui-oxid-forming metal, and then ermitting the mass to set, substantially as escribed.-

3. The process of making waterproof Portland cement mortar, which consists in first intimately mixing in a dry condition, ordinary Portland cement and unburnt sedimentary colloidal clay, then mixing the same with sand in the presence of a dilute solution of a soluble aluminium salt, and then permitting the mass to set, substantially as described.

4. The process of making waterproof Portland cement mortar, which consists in first intimately mixing in a dry condition, ordinary Portland cement and unburnt sedimentary colloidal clay, then mixing the same with sand in the presence of a solution containing between 1% and 3%of aluminium sulfate, and then permitting the mass to set, substantially as described.

5. A Waterproof Portland cement mortar, comprising sand, hydrolized ordinary Portland cement, and colloidal unburnt, highly plastic clay, all of the particles of said clay eing homogeneously distributed throughout the particles of said cement, and said mortar being free from waterproofing organic compounds in suflicient amounts to impart waterproofing roperties thereto,sub stantially as described? 6. A waterproof Portland cement mortar, comprising sand, hydrolized ordinary Portland cement, colloidal clay, all of the particles of said clay being homogeneously distributed throughout the articles of said cement, and an amount-oi a compound of a sesqui-oxid-forming metal in excess of the amount normally present in said cement, said mortar bein free from waterproofing organic compoun s in suflicient amounts to impart waterproofing properties thereto and hem free from abnormal quantities of acids or al alies, substantially as described.

7. In theprocess of making Portland'cement mortar, the step which consists in intimately mixin in a dry condition, neat ordinary Port and cement and an inorganic colloid, capable of freely flowin through dies sufiiciently small to prevent t e passage of finely divided common clay containin but small amounts of colloidal matters an corresponding in its colloid content to colloidal sedimentary clay said accomplishing a homogeneous and intimate combination of the particles of said cement and the particles of said colloid, substantially as described.

8. In the process of making Portland cement mortar, the step which consists in intimately mixing in a dry condition, neat 0rdinary Portland cement and sedimentary colloidal clay, said clay bein substantially free from sand and capable 0% freely flowing through dies sufficiently small to prevent the passage of finely divided common clay containing but small amounts of colloidal matters, whereby a homogeneous and intimate combination of the articles of said cement and the particles of said clay is obtained, substantially as described.

9. The intermediate product obtained in the process of making waterproof Portland cement mortar, which consists of anintimate, finely pulverized mixture of ordinary Portland cement and an unburnt inorganic colloid capable of freely flowing, when isolated, throug 1 dies sufliciently small to prevent the passage of finely divided common clay containing but small amounts of colloidal matters and corresponding in its colloid content to colloidal sedimentary clay, all of the particles of said inorganic colloid being homogeneously distributed throughout the particles of said cement, said mixture consisting chiefly of Portland cement, and being free from waterproofing organic compounds in suflicient amounts to impart waterproofing properties to cement mortar produced therefrom, substantially as described.

10. The intermediate product obtained in the process of making waterproof Portland cement mortar, which consists of an intimate, finely pulverized mixture of ordinary Portland cement and unburnt sedimentary, colloidal clay ca able of freely flowing through dies suflicient y small to prevent the passage of finely divided common clay containing but small amounts of colloidal matters, all of the particles of said clay being homogeneously distributed throughout the particles of said cement, said mixture consisting chiefly of Portland cement, and being free from waterproofing organic compounds in suflicient amounts to impart waterproofing properties to cement mortar roduced therefrom, substantially as descri ed.

11. In the process of making Portland cement mortar, the step which consists in mixing a cement containing chiefly ordinary Portland cement free from abnormal quantities of free alkalies, with sand in the presence of a dilute solution of a soluble salt of a I06. COMPOSITIONS,

sea-ass sesqui-oxid-forming metal and in the absence of hygroscopic salts and suflicient quantities of waterproofin organic compounds to imart waterproo g properties to the resulting cement mortar, substantially as described.

12. In the process of making Portland cement mortar, the step which consists in mixing a cement containing chiefly ordinary Portland cement free from abnormal uantities of free alkalies, with a relatively arge quantity of an inert silicious body material, in the presence of a dilute solution of a soluble salt of a ses ui-oxid-forming metal and in the absence 0 hygroscopic salts and sufficient quantities of waterproofin organic compounds to impart waterproo g pro erties to the resultin cement mortar, su stantially as described:

13. The process of making waterproof Portland cement mortar, which consists in first intimatel in a dry'condition, ordinary Port and cement. and an unburnt inor anic colloid, then mixing the same with a re atively large uantity of an inert silicious body materia in the presence of a dilute solution of a soluble salt of a ses ui-oxidforming metal, and then permitting the mass to set, substantially as described.

14. In the process of making Portland cement mortar, the step which consists in mixing a cement containing chiefly ordinary Portland cement, free from abnormal uantities of free alkalies, with a relatively arge quantity of sand,inthe resence of a 1% solution of aluminium su fate, and then per-f mittinf the mass to set, substantially as describe 15. The process of. makingl'waterproof Portland cement mortar, Whic consists in first intimatel mixing in a dry condition ordinary Port and cement and an unburnt inor anic colloid, then mixing the same with san in the presence of a dilute solution of a soluble colloiding agent, capable of formin an insoluble precipitate with the calcium oxi normally (present in the cement, and having weak aci properties,,and then permitting the mass to set, substantialllyias described.

16. The process of ma waterproof Portland cement mortar, whic consists in first intimately mixing in a dry condition ordinary Portland cement and unburnt sedimentary colloidal clay, then the same with an inert silicious body material, in the Cross Reference nature to impart waterproo hygroscopic sa ts and sufficient presence of a dilute solution of a soluble coloiding agent, capable of forming an insoluble precipitate with the calcium oxid normally present in the cement, and having weak acid pro erties, and in the absence of hygroscopic sa ts and sufiicient uantities of Waterproofing organic compoun s of a bituminous, resinous, oily, fattgnor albuminous g properties to the resulting cement mortar, substantially as described.

a 17. In the process of making Portland ce- EXAMINER ment mortar, the step which consists in mixing a cement containing chiefly ordinary Portland cement, free from abnormal uantities of free alkalies, with relatively arge quantities of an inert, silicious body material, in the' resence of a dilute solution of a soluble colloiding agent, capable of forming an insoluble precipitate with the calcium oxid normally resent in the cement, and having weak acid pro rties, and in the absence of hygroscopic sa ts and sufficient quantities of waterproofing organic compounds of a bituminous, resinous, oily, fatty or albuminous nature to impart waterproofing properties to the resulting cement mortar, su stantially as described 18. In the process of making Portland cement mortar, the step which consists in mixing a cement containing chiefly ordinary Portland cement free from abnormal uantities of free alkalies, with relatively arge uantities of an inert, silicious body mater1al,in the resence of a colloiding agent comprising a 61 ute solution of a soluble salt of a polyvalent metal, capable of forming an insoluble precipitate with the calcium oxid normally present in the cement, and having weak acid pro erties, and in the absence oi auantities of waterproofing organic compoun s of a bituminous, resinous, oily, fatty or albuminous nature to impart waterproofin qualities to the resulting cement mortar, su stantially as described.

' In testimony whereof, I have signed my name to this specification in the presence of 'two subscribing Witnesses, this twenty-second day of October 1907.

CHABLEs E. WERZ, W. H. SWENARTON. 

